Plasticized cellulose derivative



Patented July 26, 1949 PLASTICIZED CELLULOSE DERIVATIVE Maximilien Grunfeld and Emile Clement Cottet, Lyon, France, assignors to Societe des Usinea Chimiques Rhone-Poulenc, Paris, France No Drawing. Application October 22, 1945, Serial No. 623,895. In France January 24, 1941 Section 1, Public Law 690, August 8, 1946 Patent expires January 24, 1961 4 Claims. (01. 106180) 1 This invention relates to methods of using adiuvants of technical organic substances and to ence of suitable catalysts. products embodying these adjuvants with these The partial esters of pentanetriol-1-2-5 are obsubstances. tained either by partial esteriflcation of the An object of the invention is to plastify techpentanetriol, or by partial saponification of a nical and synthetic organic substances, such as tri-ester according to known methods. cellulose, cellulose derivatives, artificial and In a general way, the embodiment of natural resins, polyvinyl compounds, polymerizapentanetriol-l-2-5 or its esters with organic plastion products, condensation products, gums, tifiable substances, results in an improvement of gelatin, etc., by means of adjuvants, in order to their plastic properties and their pliancy. For produce compositions having superior qualities in each organic substance it is easy to determine, the ultimate forms of films, pellicles, varnishes, from the list of adluvants recommended accord-- sizings, coatings, adhesives, sheets, threads, ing to the present invention, the compound and sticks, tubing, moldings, and products of other proportion desirable in order to'attain the adapuseful forms and adaptations. tation providing the desired property.

A particular object of the invention is the pro- Thus, pentanetriol-l-2-5 itself is a suitable duction of compositions which in their ultimate plasticizer for materials such as regenerated celutilized forms are characterizable by new or imlulose, cellulose ethers, polyvinyl alcohol, gum proved qualities of transparency, elasticity, arable, gelatin, etc. The esters of pentanetriolflexibility, tenacity, pliability, durability, adapt- 1-2-5 can be used advantageously as plasticizers ability, brilliance, smoothness, resistance, coatof most diverse plastic-substances, such as cellug-capacity, insensltiveness to exterior condilulose derivatives, artificial resins, condensationtions, etc, as the case may be. products, polymerization products, and natural A further object of the invention is to provide eS nS- improved plastiiied compositions by the incor- However, this enumerationisnot exclusive, beporation of the adjuvants herein disclosed either cause h p s i i i i o m yin p n n riolalone or with already known adjuvants, such as and s p y Wholly esterified p o sulioamides, triaryl-phosphates, pigments, and do not involve any spe ifici y with sp to a y any of the ordinary adjuvants or auxiliaries category in which the technical organic subl own m th art, stances may be put. Besides, the search for the Another object of the invention is to provide t properties, su as sta y in t e ld improved plastifled compositions which may be rather th n th p i u plasti pr p m y tinted or pigmented, or sup lem ted it dyelead to distinctive results through the selection stufls, lampblack, titanium oxide, resins, etc., in Of One o t e Su gested adiuvants. any desirable proportions and in manners ob- The Diastification mayinsome 0886s he b h vi u t th art, about by directly associating the adiuvant and It has been found, and this finding concerns the the plastifiable m e i in other 8 y present invention, that pentanetrio1-1-2-5 and co pora-ting the intended constituents of thedeits partly or wholly esterified products, owing to ed omposi ion h he a d pp p their remarkable compatibility with most of the 40 Solvents among which he fol owing are found natural and synthetic organic compounds of the useful according to the particular case: water. types that are capable of being plasticized, are aqueous alcohol, denatured alcohol, ethyl alcohol, excellent adiuvants of these compounds. acetone, benzene, toluene, cyclop nta o Pentanetriol-1-2-5 can be conveniently prephorone, butyl acetate, butyl alcohol, ethyl acepared by hydrolytic scission of the nucleus of 5 te, e hyl lac e, met ylene chloride, and simitetrahydrofurfuryl alcohol, which is obtainable by a o e hydrogenation of furfural, an abundant and The following examples are Presented y y readily available raw materiaL p ta t i pb of illustration and are not restrictive in any way 2-5 may also be prepared by saponiflcation of a of the numerous applications ch are made pentanetriol ester, or by any other process empossible by the Present inventmn- The Parts i ployed for the production of poly-alcohols. mderstwd to be y weight" Wholly esterifled pentanetriol-1-2-5 is obtained either by esterification of the pentanetriol Example I by well known methods, or by boiling tetrahydro- 200 parts of polyvinyl alcohol of high viscosity iuriuryl alcohol or one of its partial esters with are dissolved by agitation in 800 parts or water.

, 2 A an anhydride (acetic, for instance) in the presp Example 11 60 parts of methyl-cellulose (OCH: content: l

percent) are dissolved in 940 parts of water. 18

parts of pentanetriol-i-2-5 are added to'the solution, and the latter is run on a plate, as before indicated. The film obtained is quite transparent and has good elasticity, and, from these two considerations, it is superior to unplasticized films or those plasticized otherwise. It is especially characterized by being protractable to a high degree before rupturing. I

If the plasticized solution, instead of being run on a plate, is thinned with about eight volumes of water and a net fabric is treated with the resuiting mixture, a sizing results which is remarkably flexible and tenacious. and in these respects is superior to ordinary sizings.

Example III 300 parts of an interpolyamide. obtained by copolymerization of 60 parts of adipic hexamethylenediamine and 40 parts of e-aminocapro'ic acid, are dissolved by warming in 80 percent aqueous alcohol. To the solution are added 75 parts of pentanetriol-i-2-5. The warm solution is run on a surface heated to 70 0., where, after being run, it is stoved at 80" 0. Upon drying, a transparent film is obtained which in elasticity and piiability is much superior to a film not so plasticiaed.

The plasticized solution can also be pigmented with dyes and appropriate substances (lampblack, Zapon dyestuifs, titanium oxide, etc.) and afterwards applied by a gumming machine, by a scraper, or by other known means, upon a previously smoothed fabric. A coated fabric of the moleskin type is obtained which, from the standpoint of resistance to wear and tear, is appreciably superior to similar products having coatings of linseed oil or cellulose derivatives.

Example IV I i A thin sheet of cellulose regenerated from vis case is passed through a 50 percent pentanetriol solution. After dripp ng and drying, the resulting sheet, containing about 20 percent of pentanetrioi, is very pliable and resistant and quite transparent.

Example V Example VI 250 parts of Rhodopas HH" (a polyvinyl acetate of high viscosity) are dissolved in a mixture of 600 parts oi 95 percent denatured alcohol and 150 parts of ethyl lactate. To this solution are added 50 parts of triacetate of pentanetriol-i-2-5. The varnish thus obtained can be applied on i practically any surface, and it imparts thereto a transparent, smooth and lustrous coating of very good pliancy. may also be added to the varnish.

Example VII The following are worked up at about 70' 0.: parts of "Rhovinal F" polyvinyl formal), 10 parts of triacetate of pentanetriol-l-2-5, and 70 parts of 80 percent alcohol. The composition is rolled while warm, for the removal of the solvent. The plasticized formal thus obtained is converted, according to the known celluloid technique, into transparent and flexible plastic sheets, which retain their pliancy even at very= low temperatures.

By substituting tripropionate of pentanetrioll-2-5 for the triacetate of this example, similar results are obtained.

Example VIII 100 parts of cellulose acetate.'containing about 54 percent of acetic acid, are worked up with 500 parts of acetone containing 33 parts of triacetate of pentanetriol-l-2-5. .A bright and limpid solution is obtained which, after evaporation, affords a homogeneous film which is transparent and pliant.

Example X The following are intermixed at 50 6.: 50 parts of cellulose acetate soluble in acetone, 15 parts of triacetate of pentanetriol-l-2-5, and 40 parts of a mixture consisting of equal parts by weight of ethyl alcohol and benzene. When the paste has become homogeneous it is subjected to processings known in the manufacture of plastic materials, such as rolling, baking under pressure, and cutting. Transparent sheets are obtained. and their color is unchanged by light.

In addition to triacetate of pentanetriol-l-2-5, triaryl-phosphates, sulfonamides, pigments, and any of the ordinary adjuvants known in the art of these plastic materials may be added as required or desired. Y

Example XI 20 parts of cellulose triacetate are dissolved in parts of methylene chloride containing 10 percent of alcohol. To this mixture are added 10 parts of triacetate of pentanetriol-l-2-5 while agitating. When the mixture is homogeneous, the resulting solution is filtered and run upon a level surface. After evaporation, ,a pliant and water-resistant film is obtained which can be folded a considerable number of times without impairment.

Example XII of triacetate of pentanetrlol-i-2-5 are added.

Soluble dyes. pigments and resins A varnish oi superior quality is thereby obtained. This formula can be modified conveniently to make the varnish more or less still. or to pigment Example xm 10 parts of polyvinyl chloride. molecular weight 150,000 (according to Staudinger) are dissolved in 90 parts of cyclopentanone. .2.5 parts of triacetate of pentanetriol-l-2-5 are added, and this solution is allowed to evaporate upon a thin plate in a ventilated oven. The resultant film is characterized by its pliability and pleasing transparency; whereas, without the triacetate, inflexible and crumpling films result.

Example XIV 5 parts of technical proplonate of pentanetriol-1-2-5 are added to 100 parts of a benzene solution containing 25 percent of polystyrol of high viscosity. The resulting solution is a varnish which, after evaporation, produces a flexible coating. and'it can be applied to 9. flexible material; whereas if the propionate of pentanetriol is omitted, the result is a coating that cracks.

Example XVI The following are intermixed: 100 parts of benzyl cellulose. 20 parts of triacetate of pentanetriol-1-2-5, and 80 parts of solvent (equal volumes of benzene and alcohol). When a paste is obtained, plastic sheets, or moldings, sticks and tubing, are prepared by known methods;'these articles are characterized by a good flexibility, and in unpigmented products by an excellent transparency which is particularly better than 318.1; obtained by the use of other known plase rs.

Example XVII 6 parts of triacetate of pentanetriol-1-2-5 are added to 100 parts of an alcoholic solution containing percent of colophony,and the resulting solution is spread upon the surface of a paper band. The solvent is evaporated by drying, and a coated flexible adhesive paper is thereby obtained which is much less brittle than one prepared without pentanetriol triacetate.

Example XVIII 4 grams of propionate of pentanetriol-1-2-5 are added to grams of an aqueous solution containing 20 percent of polyvinyl alcohol, saponification value 120. Upon drying, a non-sticky, flexible, slightly dull film is obtained.

It will be understood by those skilled in the art that statements herein of proportions of ingredients of the compositions exemplified, and statements of temperatures, are susceptible to appropriate modifications without departure from the spirit and scope of this invention.

It will be perceived, from the varied illustrative examples herein presented, that the methods of adaptations and modifications of organic plastifiable materials by means of the herein disclosed adjuvant pentanetriol compounds supply a wide range of products having practical utility in extensive industrial fields.

We claim:

1. A composition of matter consisting of a cellulosic derivative of the class comprising cellulose esters and cellulose ether-s plasticized with triacetate of pentanetriol 1,2,5.

2. A composition of matter consisting of cellulose acetate plasticized with triacetate of pentanetriol 1,2,5.

3. A composition of matter consisting of benzyl cellulose plasticized with triacetate of pentanetriol 1,2,5.

4. A composition of matter consisting of nitrocellulose plasticized with triacetate of pentanetriol 1,2,5.

MAXIIMILIEN GRUNFELD. EMILE CLEIVIENT COTTET.

, REFERENCES CITED The following references are of record in the 50 file of this patent:

UNITED STATES PATENTS Number Name Date 2,100,425 Bent et a]. Nov. 30, 1937 2,337,340 Meyer Dec. 21, 1943 

